WO2009035893A1 - Compositions contenant une combinaison de stéréoisomères z et e d'hydrofluorooléfines - Google Patents

Compositions contenant une combinaison de stéréoisomères z et e d'hydrofluorooléfines Download PDF

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Publication number
WO2009035893A1
WO2009035893A1 PCT/US2008/075165 US2008075165W WO2009035893A1 WO 2009035893 A1 WO2009035893 A1 WO 2009035893A1 US 2008075165 W US2008075165 W US 2008075165W WO 2009035893 A1 WO2009035893 A1 WO 2009035893A1
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Prior art keywords
isomer
combination
weight
isomers
hydrofluoroolefin
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PCT/US2008/075165
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English (en)
Inventor
Philippe Bonnet
Maher Y. Elsheikh
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Arkema Inc.
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Application filed by Arkema Inc. filed Critical Arkema Inc.
Priority to JP2010515295A priority Critical patent/JP2010531925A/ja
Priority to US12/667,115 priority patent/US20110009678A1/en
Priority to ES08799122.0T priority patent/ES2657212T3/es
Priority to CN200880023379A priority patent/CN101687733A/zh
Priority to PL08799122T priority patent/PL2185488T3/pl
Priority to EP08799122.0A priority patent/EP2185488B1/fr
Publication of WO2009035893A1 publication Critical patent/WO2009035893A1/fr
Priority to US13/939,233 priority patent/US9181154B2/en
Priority to US14/870,160 priority patent/US9890097B2/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
    • C07C17/358—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by isomerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C19/00—Acyclic saturated compounds containing halogen atoms
    • C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/38—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/38—Separation; Purification; Stabilisation; Use of additives
    • C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/38—Separation; Purification; Stabilisation; Use of additives
    • C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
    • C07C17/386—Separation; Purification; Stabilisation; Use of additives by distillation with auxiliary compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/38—Separation; Purification; Stabilisation; Use of additives
    • C07C17/389—Separation; Purification; Stabilisation; Use of additives by adsorption on solids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C21/00—Acyclic unsaturated compounds containing halogen atoms
    • C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
    • C07C21/18—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143—Halogen containing compounds
    • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
    • C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/30—Materials not provided for elsewhere for aerosols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/12—Hydrocarbons
    • C09K2205/126—Unsaturated fluorinated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/22—All components of a mixture being fluoro compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Definitions

  • the present invention relates to compositions containing a combination of Z and E stereoisomers of hydrofluorooleflns.
  • the present invention also relates to means to obtain the compositions.
  • the compositions of the present invention are useful in processes for producing cooling or heat, as heat transfer fluids, refrigerants, foam blowing agents, aerosol propellants, fire suppression, extinguishing agents and solvent applications for metal degreasing and dewatering agent.
  • CFCs chlorofluorocarbons
  • HFCs hydro fluorocarbons
  • HFC- 134a chlorofluorocarbons
  • HFC- 134a hydro fluorocarbons
  • HFC-152a pure hydrocarbons such as butane or propane
  • natural refrigerants such as CO 2 .
  • Many of these suggested replacements are, flammable, and/or have low energy efficiency. Therefore, new alternative refrigerants are being sought.
  • Fluoroolef ⁇ n materials such as hydrofluoropropene have generated interest as replacements for HFCs.
  • the inherent chemical instability of these materials in the lower atmosphere provides the low global warning potential and zero or near zero ozone depletion properties desired. However, such inherent instability is believed to also impact their toxicity.
  • the Z isomer will be much more active towards oxygen compared to the E isomer.
  • the object of the present invention is to provide novel compositions that can serve as refrigerant and heat transfer fluids as well as blowing agents, solvent cleaners etc. that provide unique characteristics to meet the demands of low or zero ozone depletion potential, lower global warming potential and low toxicity.
  • the present invention is directed toward combinations containing Z and E stereoisomers of hydro fluoroolefins where the more toxic isomer is less than 30 % weight of the combination (vs the sum of Z+E), to minimize the toxicity impact in the applications they will be used for such as cooling and heat fluids, foams blowing agents or solvents.
  • the invention is also directed toward means to obtain these combinations.
  • Hydrofluoroolefms have been proposed as heat transfer fluids as well as blowing agents, solvent cleaners etc. which exhibit a low global warming potential and zero ozone depletion value.
  • the low global warming potential is a result of the atmospheric degradation of the hydrofluoroolef ⁇ ns, typically in just a few days.
  • the fast atmospheric degradation of hydro fluoroolefins is related to reactivitiy with OH radicals.
  • Toxicity of hydro fluoroolefins varies between the geometric isomers.
  • Hydro fluoroolefins which can exist as Z and E isomers are of particular interest include:
  • a preferred ratio of Z and E isomers is less than about 30 % weight of the combination of the more toxic isomer (vs the sum of Z+E) and even more preferably less than about 10 % of the more toxic isomer. The most preferred ratio is less than about 1% of the more toxic isomer (vs the sum Z+E).
  • a preferred ratio of Z and E isomers is less than about 30 % weight of the combination of the E isomer (vs the sum of Z+E) and even more preferably less than about 10 % of the E isomer.
  • the most preferred ratio is less than about 1% of the E isomer (vs the sum Z+E).
  • a preferred ratio of Z and E isomers is less than about 30 % weight of the combination of the Z isomer (vs the sum of Z+E) and even more preferably less than about 10 % of the Z isomer.
  • the most preferred ratio is less than about 1% of the Z isomer (vs the sum Z+E).
  • the combinations of the present invention can also further include additional low global warming potential and low or zero ozone depletion value materials including but not limited to hydrocarbons such as pentane or cyclopentane, CO 2 , hydro fluorocarbons such as difluoromethane (HFC-32), 1,1,1,3 tetrafluoroethane
  • hydrocarbons such as pentane or cyclopentane, CO 2
  • hydro fluorocarbons such as difluoromethane (HFC-32), 1,1,1,3 tetrafluoroethane
  • HFC- 134a pentafluoroethane
  • HFC-152a 1,1-difluoroethane
  • hydrochloroalkenes such as M ,2-dichloroethylene (1,2-DCE).
  • fluorinated or perfluorinated solvents HFC, Hydrofluoroethers, PFC
  • oxygenated solvents such alcohols or ethers
  • N containing solvents such as amines, Cl to ClO hydrocarbons such as isobutane, butane, propane, pentane, isopentane hexane...
  • the solids could be (but are not limited to) molecular sieves, alumina, carbon sieves, zeolites and the like.
  • the preferred boiling point (bp) of the low GWP refrigerants is between -10 to -4O 0 C.
  • Refrigerant must be chemically stable during applications eg, doesn't react with active metal in the system such as aluminum, copper or iron, soluble and compatible with refrigerant oil.
  • the combinations containing Z and E stereoisomers of hydro fluoroolefins of the present invention have been found effective as replacements for high GWP (global warming potential) refrigerant in refrigeration, air-conditioning, or heat pump systems.
  • high GWP refrigerants in such systems include materials such as R134a, R22, R245fa, Rl 14, R236fa, R124, R410A, R407C, R417A, R422A, R507A, and R404A.
  • the combinations containing Z and E stereoisomers of hydro fluoroolefins of the present invention are effective working fluids in refrigeration, air-conditioning, or heat pump apparatus that uses, used or is designed to use conventional high GWP refrigerants.
  • Vapor-compression refrigeration, air-conditioning, or heat pump systems include an evaporator, a compressor, a condenser, and an expansion device.
  • a vapor- compression cycle re-uses refrigerant in multiple steps producing a cooling effect in one step and a heating effect in a different step.
  • the cycle can be described simply as follows: liquid refrigerant enters an evaporator through an expansion device, and the liquid refrigerant boils in the evaporator at a low temperature to form a gas and produce cooling.
  • the low-pressure gas enters a compressor where the gas is compressed to raise its pressure and temperature.
  • mobile refrigeration apparatus or mobile air-conditioning (MAC) apparatus refers to any refrigeration or air-conditioning apparatus incorporated into a transportation unit for the road, rail, sea or air.
  • the present invention is particularly useful for road transport refrigerating or air-conditioning apparatus, such as automobile air-conditioning apparatus or refrigerated road transport equipment.
  • the combinations containing Z and E stereoisomers of hydro fluoroolefms of the present invention may also be useful in stationary air-conditioning and heat pumps, e.g. chillers, high temperature heat pumps, residential and light commercial and commercial air-conditioning systems.
  • stationary refrigeration applications the present compositions may be useful in equipment such as domestic refrigerators, ice machines, walk-in and reach-in coolers and freezers, and supermarket systems.
  • the combinations containing Z and E stereoisomers of hydro fluoroolefms of the present invention typically will include refrigeration lubricants, i.e. those lubricants suitable for use with refrigeration, air-conditioning, or heat pump apparatus.
  • refrigeration lubricants i.e. those lubricants suitable for use with refrigeration, air-conditioning, or heat pump apparatus.
  • these lubricants are those conventionally used in compression refrigeration apparatus utilizing chlorofluorocarbon refrigerants.
  • Such lubricants and their properties are discussed in the 1990 ASHRAE Handbook, Refrigeration Systems and Applications, chapter 8, titled “Lubricants in Refrigeration Systems”.
  • Lubricants of the present invention may comprise those commonly known as "mineral oils" in the field of compression refrigeration lubrication. Mineral oils comprise paraffins (i.e.
  • Lubricants of the present invention further comprise those commonly known as "synthetic oils" in the field of compression refrigeration lubrication. Synthetic oils comprise alkylaryls (i.e. linear and branched alkyl alkylbenzenes), synthetic paraffins and napthenes, and poly(alphaolef ⁇ ns).
  • Lubricants of the present invention further comprise those that have been designed for use with hydrofluorocarbon refrigerants and are miscible with refrigerants of the present invention under compression refrigeration, air-conditioning, or heat pump apparatus' operating conditions.
  • Such lubricants include, but are not limited to, polyol esters (POEs) such as Castrol.RTM. 100 (Castrol, United Kingdom), polyalkylene glycols (PAGs) such as RL-488A from Dow (Dow Chemical, Midland, Mich.), and polyvinyl ethers (PVEs). These lubricants are readily available from various commercial sources.
  • the preferred combinations of the present invention will typically have boiling points between about— 40° C to 60° C and be compatible with the A side, the B side or both and typically are liquid at atmospheric pressure from about 10° C to 50° C and more preferably 30° C to 40° C and provide a foam with good dimensional stability.
  • the combinations have a low thermal conductivity and provide a foam with low thermal conductivity.
  • the preferred combinations of the present invention will have boiling points less than the melt and/or glass transition temperature of the polymer resin, typically less than about 100°C, preferably between about -4O 0 C to about 10 0 C.
  • the process for preparing a foamed thermoplastic product is as follows: Prepare a foamable polymer composition by blending together components comprising foamable polymer composition in any order. Typically, prepare a foamable polymer composition by plasticizing a polymer resin and then blending in components of a blowing agent composition at an initial pressure.
  • a common process of plasticizing a polymer resin is heat plasticization, which involves heating a polymer resin enough to soften it sufficiently to blend in a blowing agent composition.
  • heat plasticization involves heating a thermoplastic polymer resin near or above its glass transition temperature (Tg), or melt temperature (Tm) for crystalline polymers.
  • a foamable polymer composition can contain additional additives such as nucleating agents, cell-controlling agents, dyes, pigments, fillers, antioxidants, extrusion aids, stabilizing agents, antistatic agents, fire retardants, IR attenuating agents and thermally insulating additives.
  • Nucleating agents include, among others, materials such as talc, calcium carbonate, sodium benzoate, and chemical blowing agents such azodicarbonamide or sodium bicarbonate and citric acid.
  • IR attenuating agents and thermally insulating additives include carbon black, graphite, silicon dioxide, metal flake or powder, among others.
  • Flame retardants can include, among others, brominated materials such as hexabromocyclodecane and polybrominated biphenyl ether.
  • Foam preparation processes of the present invention include batch, semi-batch, and continuous processes. Batch processes involve preparation of at least one portion of the foamable polymer composition in a storable state and then using that portion of foamable polymer composition at some future point in time to prepare a foam.
  • a semi-batch process involves preparing at least a portion of a foamable polymer composition and intermittently expanding that foamable polymer composition into a foam all in a single process.
  • U.S. Pat. No. 4,323,528, herein incorporated by reference discloses a process for making polyolefin foams via an accumulating extrusion process.
  • the process comprises: 1) mixing a thermoplastic material and a blowing agent composition to form a foamable polymer composition; 2) extruding the foamable polymer composition into a holding zone maintained at a temperature and pressure which does not allow the foamable polymer composition to foam; the holding zone has a die defining an orifice opening into a zone of lower pressure at which the foamable polymer composition foams and an openable gate closing the die orifice; 3) periodically opening the gate while substantially concurrently applying mechanical pressure by means of a movable ram on the foamable polymer composition to eject it from the holding zone through the die orifice into the zone of lower pressure, and 4) allowing the ejected foamable polymer composition to expand to form the foam.
  • a continuous process involves forming a foamable polymer composition and then expanding that foamable polymer composition in a non-stop manner.
  • prepare a foamable polymer composition in an extruder by heating a polymer resin to form a molten resin, blending into the molten resin a blowing agent composition at an initial pressure to form a foamable polymer composition, and then extruding that foamable polymer composition through a die into a zone at a foaming pressure and allowing the foamable polymer composition to expand into a foam.
  • cool the foamable polymer composition after addition of the blowing agent and prior to extruding through the die in order to optimize foam properties. Cool the foamable polymer composition, for example, with heat exchangers.
  • Foams of the present invention can be of any form imaginable including sheet, plank, rod, tube, beads, or any combination thereof. Included in the present invention are laminate foams that comprise multiple distinguishable longitudinal foam members that are bound to one another.
  • the present invention relates to blowing agent combinations containing Z and E stereoisomers of hydro fluoroolef ⁇ ns as described herein for use in preparing foams.
  • the invention provides foamable compositions, and preferably polyurethane, polyisocyanate and thermoplastic foam compositions, and method of preparing foams.
  • one or more of the present hydro fuoroolef ⁇ ns with stabilizer combinations are included as a blowing agent in foamable compositions, which composition preferably includes one or more additional components capable of reacting and foaming under the proper conditions to form a foam or cellular structure. Any of the methods well known in the art may be used or adapted for use in accordance with the foam embodiments of the present invention.
  • the present invention further relates to a method of forming a foam comprising: (a) adding to a foamable composition a combinations containing Z and E stereoisomers of hydro fluoroolefins of the present invention; and (b) reacting the foamable composition under conditions effective to form a foam.
  • Another embodiment of the present invention relates to the use of the combinations containing Z and E stereoisomers of hydro fluoroolefins as described herein for use as propellants in sprayable compositions. Additionally, the present invention relates to a sprayable composition comprising the combinations containing Z and E stereoisomers of hydrofluoroolefins as described herein.
  • the active ingredient to be sprayed together with inert ingredients, solvents and other materials may also be present in a sprayable composition.
  • the sprayable composition is an aerosol.
  • Suitable active materials to be sprayed include, without limitations, cosmetic materials, such as deodorants, perfumes, hair sprays, cleaners, and polishing agents as well as medicinal materials such as anti-asthma and anti-halitosis medications.
  • the present invention further relates to a process for producing aerosol products comprising the step of adding combinations containing Z and E stereoisomers of hydrofluoroolefins as described herein to active ingredients in an aerosol container, wherein said composition functions as a propellant.
  • a further aspect provides methods of suppressing a flame, said methods comprising contacting a flame with a fluid comprising a combinations containing Z and E stereoisomers of hydrofluoroolefins of the present invention.
  • Any suitable methods for contacting the flame with the present composition may be used.
  • a combinations containing Z and E stereoisomers of hydrofluoroolefins of the present invention may be sprayed, poured, and the like onto the flame, or at least a portion of the flame may be immersed in the flame suppression composition.
  • those of skill in the art will be readily able to adapt a variety of conventional apparatus and methods of flame suppression for use in the present invention.
  • a further embodiment provides methods of extinguishing or suppressing a fire in a total-flood application comprising providing an agent comprising a combinations containing Z and E stereoisomers of hydrofluoroolefins of the present invention; disposing the agent in a pressurized discharge system; and discharging the agent into an area to extinguish or suppress fires in that area.
  • Another embodiment provides methods of inerting an area to prevent a fire or explosion comprising providing an agent comprising a combinations containing Z and E stereoisomers of hydrofluoroolefins of the present invention; disposing the agent in a pressurized discharge system; and discharging the agent into the area to prevent a fire or explosion from occurring.
  • a detector is usually used to detect an expanding fireball from an explosion, and the agent is discharged rapidly to suppress the explosion.
  • Explosion suppression is used primarily, but not solely, in defense applications.
  • a combination containing Z and E stereoisomers of hydrofluoroolefins of the present invention is discharged into a space to prevent an explosion or a fire from being initiated.
  • a system similar or identical to that used for total-flood fire extinguishment or suppression is used.
  • a dangerous condition for example, dangerous concentrations of flammable or explosive gases
  • combination containing Z and E stereoisomers of hydrofluoroolefins of the present invention is then discharged to prevent the explosion or fire from occurring until the condition can be remedied.
  • the extinguishing method can be carried out by introducing the composition into an enclosed area surrounding a fire. Any of the known methods of introduction can be utilized provided that appropriate quantities of the composition are metered into the enclosed area at appropriate intervals.
  • a composition can be introduced by streaming, e.g. using conventional portable (or fixed) fire extinguishing equipment; by misting; or by flooding, e.g., by releasing (using appropriate piping, valves, and controls) the composition into an enclosed area surrounding a fire.
  • the composition can optionally be combined with an inert propellant, e.g., nitrogen, argon, decomposition products of glycidyl azide polymers or carbon dioxide, to increase the rate of discharge of the composition from the streaming or flooding equipment utilized.
  • the extinguishing process involves introducing a combination containing Z and E stereoisomers of hydro fluoroolefins of the present invention to a fire or flame in an amount sufficient to extinguish the fire or flame.
  • a combination containing Z and E stereoisomers of hydro fluoroolefins of the present invention to a fire or flame in an amount sufficient to extinguish the fire or flame.
  • the amount of flame suppressant needed to extinguish a particular fire will depend upon the nature and extent of the hazard.
  • test data is useful in determining the amount or concentration of flame suppressant required to extinguish a particular type and size of fire.
  • the ideal hydrofluoroolefin suitable for solvent applications, should have bp between 21-60 0 C.
  • the product should be chemically stable in contact with metals, doesn't swell upon exposure to various plastic such as acrylonitrile butadiene styrene, PVC, polybutyelene tetraphathlate, polyethylene HD, polyethylene LD, polymethyle methacrylate, polyethylene, high impact polystyrene, polystyrene crystals, polystyrene 1160, polypropylene, polyamide 11, polycarbonate, polyvinylidene fluoride, polyetehrer block amide; or elastomeric material such as styrene butadiene 6510, ethylene propylene EP710, hydrogenated nitrile7DT1566, polychloroprene N658, polyacrylates DA 65, hyplalon DH70, fluorocarbon df, nitrile PB701, silicone SL1002,
  • compositions containing a combination of Z and E stereoisomers of hydrofluoroolefin could be use in combination with a stabilizer or stabilizers selected from free radical scavengers, acid scavengers, oxygen scavengers, polymerization inhibitors, corrosion inhibitors and combinations thereof.

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  • Materials Engineering (AREA)
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  • Combustion & Propulsion (AREA)
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  • Polymers & Plastics (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Detergent Compositions (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention porte sur les combinaisons contenant des stéréoisomères Z et E d'hydrofluorooléfines, l'isomère le plus toxique représentant environ moins de 30 % en poids de la combinaison (en fonction de la somme de Z+E), pour minimiser l'impact de toxicité dans les applications, pour lesquelles elles seront utilisées, fluides de refroidissement et de chauffage, agents de progènes moussants ou solvants. L'invention porte également sur des moyens pour obtenir des combinaisons contenant des stéréoisomères Z et E d'hydrofluorooléfines.
PCT/US2008/075165 2007-09-13 2008-09-04 Compositions contenant une combinaison de stéréoisomères z et e d'hydrofluorooléfines WO2009035893A1 (fr)

Priority Applications (8)

Application Number Priority Date Filing Date Title
JP2010515295A JP2010531925A (ja) 2007-09-13 2008-09-04 ヒドロフルオロオレフィンのｚ立体異性体とｅ立体異性体との組合せを含有する組成物
US12/667,115 US20110009678A1 (en) 2007-09-13 2008-09-04 Compositions containing a combination of z and e stereoisomers of hydrofluoroolefins
ES08799122.0T ES2657212T3 (es) 2007-09-13 2008-09-04 Composiciones que contienen una combinación de estereoisómeros Z y E de hidrofluoroolefinas
CN200880023379A CN101687733A (zh) 2007-09-13 2008-09-04 包含氢氟烯烃的z和e立体异构体的组合的组合物
PL08799122T PL2185488T3 (pl) 2007-09-13 2008-09-04 Kompozycje zawierające połączenie stereoizomerów Z i E fluorowodoroolefin
EP08799122.0A EP2185488B1 (fr) 2007-09-13 2008-09-04 Compositions contenant une combinaison de stéréoisomères z et e d'hydrofluorooléfines
US13/939,233 US9181154B2 (en) 2007-09-13 2013-07-11 Method of obtaining a combination of Z and E stereoisomers of hydrofluoroolefins
US14/870,160 US9890097B2 (en) 2007-09-13 2015-09-30 Method of obtaining a combination of Z and E stereoisomers of 1-chloro-3,3,3-trifluoropropene

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WO2009064022A3 (fr) * 2007-11-16 2009-07-09 Daikin Ind Ltd Procédé de production de pentafluoropropène
US9026124B2 (en) 2009-03-31 2015-05-05 Futurewei Technologies, Inc. System and method for interference mitigation in a wireless communications system
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US9624148B2 (en) * 2009-10-15 2017-04-18 Mexichem Amanco Holding S.A. De C.V. Process for purifying (hydro)fluoroalkenes
US9790152B2 (en) 2009-10-15 2017-10-17 Mexichem Amanco Holding S.A. De C.V. Process for purifying (hydro)fluoroalkenes
WO2014158663A1 (fr) 2013-03-13 2014-10-02 Arkema Inc. Procédés de purification et de stabilisation d'hydrofluorooléfines et d'hydrochlorofluorooléfines
EP2970059A4 (fr) * 2013-03-13 2016-10-05 Arkema Inc Procédés de purification et de stabilisation d'hydrofluorooléfines et d'hydrochlorofluorooléfines
US10022576B2 (en) 2013-03-13 2018-07-17 Arkema Inc. Methods for purifying and stabilizing hydrofluoroolefins and hydrochlorofluoroolefins
US10215455B2 (en) 2013-08-14 2019-02-26 Central Glass Company, Limited Heat transmission method and high-temperature heat pump device
US10370313B2 (en) 2016-02-26 2019-08-06 AGC Inc. Manufacturing method of purified 1-chloro-2,3,3,3-Tetrafluoropropene and purified 1-chloro-2,3,3,3-tetrafluoropropene (Z)

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KR20100017987A (ko) 2010-02-16
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ES2657212T3 (es) 2018-03-02
PL2185488T3 (pl) 2018-04-30
CN101687733A (zh) 2010-03-31
US20130296617A1 (en) 2013-11-07
US9181154B2 (en) 2015-11-10
EP2185488A1 (fr) 2010-05-19
JP2015212263A (ja) 2015-11-26
CN105859516A (zh) 2016-08-17
US9890097B2 (en) 2018-02-13
JP2013100544A (ja) 2013-05-23
US20110009678A1 (en) 2011-01-13
EP2185488A4 (fr) 2012-03-21
KR20110133616A (ko) 2011-12-13
US20160016868A1 (en) 2016-01-21

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